JPS63117057A - Flame-retardant, heat-resistant aromatic vinyl resin composition - Google Patents
Flame-retardant, heat-resistant aromatic vinyl resin compositionInfo
- Publication number
- JPS63117057A JPS63117057A JP26140786A JP26140786A JPS63117057A JP S63117057 A JPS63117057 A JP S63117057A JP 26140786 A JP26140786 A JP 26140786A JP 26140786 A JP26140786 A JP 26140786A JP S63117057 A JPS63117057 A JP S63117057A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- arom
- vinyl resin
- heat
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 21
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000011342 resin composition Substances 0.000 title claims description 7
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000010452 phosphate Substances 0.000 claims abstract description 15
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 8
- 239000001205 polyphosphate Substances 0.000 claims abstract description 8
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- IYBPIDAYDPNCTP-UHFFFAOYSA-N 1-methyl-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(C)C(=O)C=C1C1=CC=CC=C1 IYBPIDAYDPNCTP-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 maleimide compound Chemical class 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 claims description 3
- 230000000704 physical effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 abstract description 4
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 abstract description 4
- SXTILEHINBCKSS-UHFFFAOYSA-N 1-chloro-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(Cl)C(=O)C=C1C1=CC=CC=C1 SXTILEHINBCKSS-UHFFFAOYSA-N 0.000 abstract description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 3
- 239000000178 monomer Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000005526 organic bromine compounds Chemical class 0.000 description 3
- 150000002896 organic halogen compounds Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002341 toxic gas Substances 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZVVPYIDRZJUCED-UHFFFAOYSA-N (2-oxo-1,3,2lambda5-benzodioxaphosphol-2-yl) dihydrogen phosphate Chemical compound C1=CC=C2OP(OP(O)(=O)O)(=O)OC2=C1 ZVVPYIDRZJUCED-UHFFFAOYSA-N 0.000 description 1
- FPDOHAABWLBAKE-UHFFFAOYSA-N 1-bromo-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(Br)C(=O)C=C1C1=CC=CC=C1 FPDOHAABWLBAKE-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- BAWHYOHVWHQWFQ-UHFFFAOYSA-N 1-naphthalen-1-ylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC2=CC=CC=C12 BAWHYOHVWHQWFQ-UHFFFAOYSA-N 0.000 description 1
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は従来の生活用品、事務機器などのイ◇
ンテリア、エフステリア製邑外に電器部品、電子部品等
の分野に使用される難燃性と耐熱性とを兼ね備えた芳香
族ビニル系樹脂組成物に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention is a flame-retardant product used in the fields of interiors of conventional household goods and office equipment, electrical parts, electronic parts, etc. The present invention relates to an aromatic vinyl resin composition that has both heat resistance and heat resistance.
従来ポリスチレン、ＡＢＳｍ脂などの芳香族ビニル樹脂
は機械的強度、成形加工性、耐薬品性、透明性などに優
れた特性があるため、生活用品、事務機器などに広く使
用されているが、熱変形温度が低く可燃性であるという
欠点があるため電器部品、電子部品などの分野ではそれ
らの欠点を改良すべく種々な方法が提案されている。Traditionally, aromatic vinyl resins such as polystyrene and ABSm resins have excellent properties such as mechanical strength, moldability, chemical resistance, and transparency, and are widely used in household goods and office equipment. Since it has drawbacks such as low deformation temperature and flammability, various methods have been proposed in the fields of electrical appliance parts, electronic parts, etc. to improve these drawbacks.
そのためこれらの可燃性樹脂を難燃化するために有機ハ
ロゲン化合物テトラブロモビスフェールＡ、ｆカブロモ
ビスフェノールエーテル、ヘキサブロモベンゼンや従来
から使用されている有機燐化合物トリフェニルホスフェ
ート、クレジルシフエールホスフェート、キシレニルジ
フェニルホスフェート、トリクレジルホスフェート、ト
リキシレニルホスフェートや無ｉｆｉ化６物水酸化アル
ミニウム、水酸化マグネシウムなどの難燃剤が使用され
ている。Therefore, in order to make these flammable resins flame retardant, organic halogen compounds such as tetrabromobisphenol A, f-cabromobisphenol ether, and hexabromobenzene, as well as conventionally used organic phosphorus compounds such as triphenyl phosphate, cresyl cyphere phosphate, and Flame retardants such as xylenyl diphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, non-ifi 6 compound aluminum hydroxide, and magnesium hydroxide are used.
芳香族ビニル系樹脂を難燃化するために上記のような有
機燐化合物や無機化合物は通常の添加量例えば芳香族ビ
ニル系樹脂１００重量部に対して５〜２０重量部では充
分な効果が得られず、米国難燃規制（ＵＩ、−９４規格
）の燃焼試験でＶ−ｔＫ合格するのが困難である。In order to make the aromatic vinyl resin flame retardant, the organic phosphorus compounds and inorganic compounds mentioned above can be used in the usual amount, for example, 5 to 20 parts by weight per 100 parts by weight of the aromatic vinyl resin, to obtain a sufficient effect. Therefore, it is difficult to pass V-tK in the combustion test of the U.S. Flame Retardant Regulations (UI, -94 standard).
さらに上記のような難燃剤を多量に使用すれば難燃性は
上記ＵＬ−９４規格に合格しても、耐熱性その他の物性
が著しく低下し、実用に供し得ない成形品となる。Furthermore, if a large amount of the above flame retardant is used, even if the flame retardance passes the above-mentioned UL-94 standard, the heat resistance and other physical properties will be significantly reduced, resulting in a molded product that cannot be put to practical use.
従って従来は上記の理由により、芳香族ビニル系樹脂の
難燃化にはテトラブロモビスフェノールＡ１デカブロム
ビフエニルエーテルなどの有機臭素化合物が使用されて
いる。Therefore, conventionally, organic bromine compounds such as tetrabromobisphenol A1 decabromo biphenyl ether have been used to make aromatic vinyl resins flame retardant for the above reasons.
しかしながらこれらの有機臭素化合物を使用することに
よってＵＬ−９４規格のＶ−１，Ｖ−０に合格する成形
品が得られるが有機臭素化合物は燃焼時において臭化水
素などの有毒性ガスを発生することと、成形時において
熱負荷により発生する臭化水素ガスが金型のスクリュー
を腐食させるなどの欠点がある。そのため芳香族ビニル
系樹脂組成物成形品が実用に供し得る物性を有強く要望
されている。However, by using these organic bromine compounds, molded products that pass V-1 and V-0 of the UL-94 standard can be obtained, but organic bromine compounds generate toxic gases such as hydrogen bromide when burned. Another drawback is that hydrogen bromide gas generated by heat load during molding corrodes the screws of the mold. Therefore, there is a strong demand for molded articles of aromatic vinyl resin compositions to have physical properties that can be put to practical use.
本発明は前記各方面からの要望に応え、有機ハロゲン化
合物を配合することなく、得られたＦＲＭが従来使用さ
れていた難燃剤の添加量で高度の難燃性と耐熱性及びそ
の他の優れた物性を有するＦＲＭを提供することを目的
とするものである。The present invention has been developed in response to the demands from the above-mentioned fields, and the obtained FRM has high flame retardancy, heat resistance, and other excellent properties at the added amount of flame retardant used conventionally, without adding organic halogen compounds. The purpose is to provide an FRM with good physical properties.
近年芳香族ビニル系樹脂の耐熱性の向上に関して種々の
方法が検討されている。その中でも本ド環を含有させて
耐熱性を向上させる方法が本発明の目的の達成に対して
最も効果を奏し注目に値するものである。即ち本発明者
等はイミド化合物で変性された耐熱性芳香族ビニル系樹
脂に関して更に突込んで研究を進めた結果、イミさせ得
ることを見出したのである。更に本発明者等は該難燃性
が向上した樹脂をＵＬ−９４規格のＶ−Ｏ，Ｖ−＋に合
格させるために鋭意研究した結果、有害な有機ハロゲン
化合物を使用することなく芳香族ホスフェート又１−ｊ
／及び芳香族ポリことＫより上記目的が達成されること
を確認して本発明を完成するに至った。In recent years, various methods have been studied for improving the heat resistance of aromatic vinyl resins. Among these, the method of improving heat resistance by incorporating the present do ring is most effective in achieving the object of the present invention and is worthy of attention. That is, the present inventors conducted further research on heat-resistant aromatic vinyl resins modified with imide compounds, and as a result, discovered that they could be imized. Furthermore, as a result of intensive research in order to make the resin with improved flame retardancy pass the V-O and V-+ standards of UL-94, the present inventors found that aromatic phosphate can be produced without using harmful organic halogen compounds. Also 1-j
The present invention has been completed by confirming that the above object can be achieved by / and aromatic poly(K).
本発明はマレイミド化合物で変性された耐熱性芳香族ビ
ニル系樹脂に芳香族ホスフェート又ｔ−１／及び芳香族
ポリホスフェートを配合させてなるＦＲＭを提供するも
のである。The present invention provides an FRM in which aromatic phosphate or t-1/ and aromatic polyphosphate are blended with a heat-resistant aromatic vinyl resin modified with a maleimide compound.
本発明に使用される芳香族ビニル系樹脂を形成するモノ
マー類としてはスチレン、α−メチルスチレン、アクリ
ロニトリル、メタアクリロニトリル、アクリル酸メチル
、メタクリル酸メチル等があり、またこれらのモノマー
類以外にグラフト重合させる目的で使用されるポリブタ
ジェン等がある。Monomers forming the aromatic vinyl resin used in the present invention include styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, etc. In addition to these monomers, graft polymerization Polybutadiene, etc., are used for the purpose of
本発明に使用されるマレイミド基含有化合物としてはマ
レイミド、Ｎ−メチルマレイミド、Ｎ−エチルマレイミ
ド、Ｎ−プロピルマレイミド、Ｎ ｔｃｒｔブチルマ
レイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−ラウリ
ルマレイミド、Ｎ−フェニルマレイミド、Ｎ−メチルフ
ェニルマレイミド、Ｎ−ジメチルフェニルマレイミド、
Ｎ−ナフチルマレイミドがあり、また必要に応じてＮ−
クロロフェニルマレイミド、Ｎ−ジクロロフェニルマレ
イミド、Ｎ−）ジクロロフェニルマレイミド、Ｎ−ブロ
モフェニルマレイミド、Ｎ−ジクロロフェニルマレイミ
ド、Ｎ−）！Ｊジブロモェニルマレイミドなどのハロゲ
ン含有マレイミド化合物も使用することができる。Maleimide group-containing compounds used in the present invention include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Ntcrtbutylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-phenylmaleimide, N- -methylphenylmaleimide, N-dimethylphenylmaleimide,
N-naphthylmaleimide and optionally N-
Chlorophenylmaleimide, N-dichlorophenylmaleimide, N-)dichlorophenylmaleimide, N-bromophenylmaleimide, N-dichlorophenylmaleimide, N-)! Halogen-containing maleimide compounds such as J dibromogenyl maleimide can also be used.
マレイミド化合物と本発明のモノマー類との共重合はア
ビビスイソブチロニトリル、過酸化ベンゾイル、過酸化
アンモニウム等の従来から存在するラジカル開始剤を添
加し、公知の重合方法例えば乳化重合、懸濁重合、溶液
重合などの方法が用いられる。Copolymerization of the maleimide compound and the monomers of the present invention is carried out by adding a conventionally existing radical initiator such as abibisisobutyronitrile, benzoyl peroxide, ammonium peroxide, etc., and using a known polymerization method such as emulsion polymerization or suspension polymerization. Methods such as polymerization and solution polymerization are used.
これらのマレイミド化合物は樹脂１００重量部中１〜５
０重量部、好ましくは５〜２０重量部の割合で含有させ
ることによって所望の耐熱性を付与することができる。These maleimide compounds are contained in an amount of 1 to 5 in 100 parts by weight of the resin.
By containing it in an amount of 0 parts by weight, preferably 5 to 20 parts by weight, desired heat resistance can be imparted.
１重量％未満では充分な耐熱性が得られず、５０！ｔ％
を超過して配合しても差し支えないが得られた樹脂の耐
熱性はそれ以上は向上しないため経済的な理由からその
上限を５０重量％とした０
本発明に使用される芳香族ホスフェート又は芳香族ポリ
ホスフェートとしてはトリフェニルホスフェート、トリ
クレジルホスフェート、トリキシレニルホスフェート、
トリイソプロピルフェニルホスフェート、クレジルフェ
ニルホスフェート、イングロビルフェニルジフェニルホ
ス７エート、キシレニルジフェニルホスフェート、フチ
ルフェニルジフェニルホスフエート、テトラフェニルフ
ェニレンジホスフェート、テトラクレジルフェニレンジ
ホスフェート、ポリフェニルポリフェニレンホスフェー
トなどがある。If it is less than 1% by weight, sufficient heat resistance cannot be obtained, and 50! t%
There is no problem even if it is blended in an amount exceeding 50% by weight, but the heat resistance of the resulting resin will not improve any further.For economic reasons, the upper limit was set at 50% by weight.0 Aromatic phosphate or aromatic aromatic used in the present invention Group polyphosphates include triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate,
Triisopropylphenyl phosphate, cresyl phenyl phosphate, inglobylphenyl diphenyl phosphate 7ate, xylenyl diphenyl phosphate, phthylphenyl diphenyl phosphate, tetraphenylphenyl diphosphate, tetracresyl phenylene diphosphate, polyphenyl polyphenylene phosphate, etc. be.
芳香族ホスフェート又は／及び芳香族ポリホスフェート
はマレイミド基含有芳香族ビニル系樹脂１００重量部に
対し、１〜３０重量部好ましくは５〜２０重量部の割合
で組成物中に含有される。The aromatic phosphate and/or aromatic polyphosphate is contained in the composition in an amount of 1 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the maleimide group-containing aromatic vinyl resin.
１重量％未満の場合は充分な難燃効果が得られない、ま
た３０重量部を超過すると難燃性に対しては差し支えな
いが得られた樹脂の物性が低下する欠点がある。樹脂組
成物中に得られるＦＲＭの物性に悪影響を及ぼさない範
囲で酸化防止剤、顔料、充填剤などを添加してもよい。If it is less than 1% by weight, a sufficient flame retardant effect cannot be obtained, and if it exceeds 30 parts by weight, there is no problem with flame retardancy, but there is a disadvantage that the physical properties of the resulting resin deteriorate. Antioxidants, pigments, fillers, etc. may be added to the resin composition within a range that does not adversely affect the physical properties of the FRM obtained.
又ハロゲン含有化合物は上記のようにその使用において
発生するハロゲン化水素が問題にならないような場合に
のみ上記の燐含有化合物、三酸化アンチモンなどの難燃
助剤とともに併用してもよい。Further, the halogen-containing compound may be used in combination with the above-mentioned phosphorus-containing compound, antimony trioxide, and other flame retardant aids only when the hydrogen halide generated during its use does not pose a problem, as described above.
本発明のＦＲＭｉｊイミド環含有芳香族ビニル系樹脂に
芳香族ホスフェート又は／及び芳香族ポリホスフェート
を加え混合若しくは混練した後、押出機、射出成型機な
どてより所望の形状Ｋｌｔ形することができる。After adding an aromatic phosphate or/and an aromatic polyphosphate to the FRMij imide ring-containing aromatic vinyl resin of the present invention and mixing or kneading, it can be molded into a desired shape using an extruder, an injection molding machine, or the like.
また得られた成形品は難燃性と耐熱性が共て良好であり
、しかも有害になる程度のハロゲン元素を含有しないの
で燃焼時の有毒性ガスの発生や成形時の金型スクリュー
の腐食という不都合な問題を生ずることが皆無である。In addition, the obtained molded product has good flame retardancy and heat resistance, and does not contain harmful halogen elements, so there is no risk of generating toxic gas during combustion or corrosion of mold screws during molding. There are no inconvenient problems.
次に実施例によって本発明を説明する。 Next, the present invention will be explained by examples.
実施例１
（１）共重合体（１−ａ）の製造
攪拌機及び還流冷却管を備えた重合槽にイオン交換水５
００部、過硫酸アンモニウム０．５部、亜硫酸水素ナト
リウム１．０部、ラウリル硫酸ナトリウム２部を仕込み
窒素で置換して温度を６０℃に保持した。単量体組成を
第１表の（＋−ａ）に示したスチレン５０部、アクリロ
ニトリル３０部、フェニルマレイミド１０部、α−メチ
ルスチレンｌＯ部連鎖移動剤、ドデシルメルカプタン０
．４部の混合液を５時間にわたり連続的に重合槽に供給
した後８時間熟成を行ない、反応を停止しラテックス（
１−ａ）を得た。重合率はラテックスの固形分の重量測
定より９８％であった。Example 1 (1) Production of copolymer (1-a) A polymerization tank equipped with a stirrer and a reflux condenser was charged with 5 liters of ion-exchanged water.
0.00 parts of ammonium persulfate, 1.0 part of sodium bisulfite, and 2 parts of sodium lauryl sulfate were charged, and the temperature was maintained at 60° C. by purging with nitrogen. The monomer composition is shown in (+-a) in Table 1: 50 parts of styrene, 30 parts of acrylonitrile, 10 parts of phenylmaleimide, 10 parts of α-methylstyrene chain transfer agent, 0 parts of dodecyl mercaptan.
．． After 4 parts of the mixed solution was continuously fed into the polymerization tank for 5 hours, it was aged for 8 hours, the reaction was stopped, and the latex (
1-a) was obtained. The polymerization rate was 98% as determined by weight measurement of the solid content of the latex.
（Ｉｉ） グラフト共重合体（＋−ｂ）の製造（１）
と同様な形式の重合槽にイオン交換水１３０部、ポリブ
タジェンラテックスを固形分換算で５０部、オレイン酸
ナトリウム０．４部を仕込み窒素置換して＠夏を７０℃
に保持した。単量体組成が第１表の（１−ｂ）に示した
スチレン３５部、アクリロニトリル１５部及び連鎖移動
剤ドデシルメルカプタン０．４部の混合液を５時間にわ
たり連続的に重合槽へ供給した後、熟成を２時間行ない
、反応を停止し、ラテックス（１−ｂ）を得た。重合率
はラテックスの固形分の重量測定から９８％であった。(Ii) Production of graft copolymer (+-b) (1)
130 parts of ion-exchanged water, 50 parts of polybutadiene latex in terms of solid content, and 0.4 parts of sodium oleate were placed in a polymerization tank of the same type as above, replaced with nitrogen, and heated to 70°C in the summer.
was held at After continuously feeding a mixed solution of 35 parts of styrene, 15 parts of acrylonitrile, and 0.4 parts of chain transfer agent dodecyl mercaptan to the polymerization tank for 5 hours, the monomer composition is shown in (1-b) in Table 1. After aging for 2 hours, the reaction was stopped and latex (1-b) was obtained. The polymerization rate was 98% based on the weight measurement of the solid content of the latex.
共重合体（＋−ａ）と（＋−ｂ）とのラテックスを固形
分換算でそれぞれ６０部、４０部の比率で混合した後、
２％硫酸アルミニウム水溶液中へ滴下して凝固せしめた
後、脱水乾燥した。After mixing latexes of copolymers (+-a) and (+-b) at a ratio of 60 parts and 40 parts, respectively, in terms of solid content,
The mixture was dropped into a 2% aqueous aluminum sulfate solution to solidify, and then dehydrated and dried.
得られた樹脂の酸素指数（０工）は２１１であった。The oxygen index (0 engineering) of the obtained resin was 211.
第１表ＫＯＩの測定結果を示した。Table 1 shows the measurement results of KOI.
ここに Ｏ工＝ｎ透翳脣１ＸＩＱＯ（％）で示す。Here, it is shown as O engineering = n transparent shadow 1XIQO (%).
樹脂１００重量部に対し難燃剤としてトリフェニルホス
フェ−）１５部を配合し、押出機にてベレット化してか
ら射出成形機により試験片を作成し特性を評価した。第
２表に難燃性及び物性の試験結果を示す。15 parts of triphenyl phosphate was added as a flame retardant to 100 parts by weight of the resin, and the mixture was formed into pellets using an extruder, and then test pieces were prepared using an injection molding machine and their properties were evaluated. Table 2 shows the test results for flame retardancy and physical properties.
実施例２〜４
第１表に示した実施例１の（１−ａ ） 、（１−ｂ）
の単量体及び難燃剤の代りに各々（２−ａ）〜（４〜ａ
）、 （２−ｂ） 〜（４−ｂ）の単量体及び難燃剤を
用いたこと以外は実施例１と同様の方法で試験片の特性
値を評価した。Examples 2 to 4 (1-a) and (1-b) of Example 1 shown in Table 1
(2-a) to (4-a) in place of the monomer and flame retardant, respectively.
), (2-b) to (4-b) The characteristic values of the test pieces were evaluated in the same manner as in Example 1, except that the monomers and flame retardants were used.
また比較例１〜３として表−１に示した（比１−ａ）〜
（比８−ａ）、（比１−ｂ）〜（比３−ｂ）の単量体及
び難燃剤を用いた以外は実施例１と同様の方法で試験片
を得てその性能を評価した。Also shown in Table 1 as Comparative Examples 1 to 3 (ratio 1-a) to
Test pieces were obtained in the same manner as in Example 1, except that the monomers and flame retardants of (Ratio 8-a), (Ratio 1-b) to (Ratio 3-b) were used, and their performance was evaluated. .
第２表に難燃性及び物性の試験結果を示した。Table 2 shows the test results for flame retardancy and physical properties.
実施例５
実施例１の（１）と同様な形式の重合槽にシクロヘキサ
ノンＳＯＯ部、過酸化ベンゾイルと単量体としてスチレ
ン７０部、アクリロニトリル２０部、フェニルマレイミ
ド１０部を仕込み、窒素置換して６０℃に温度を保持し
て１０時間にわたり重合させた。得られた反応生成物を
エチルエーテルに投入しポリマーを析出沈澱させた。沈
澱物を脱水乾燥した。得られた樹脂のＯＩは２０．５’
であった。第８表に測定結果を示した。Example 5 Cyclohexanone SOO, benzoyl peroxide, and 70 parts of styrene as monomers, 20 parts of acrylonitrile, and 10 parts of phenylmaleimide were charged into a polymerization tank of the same type as in (1) of Example 1, and the tank was purged with nitrogen to 60 parts. The temperature was maintained at 0.degree. C. for 10 hours. The obtained reaction product was poured into ethyl ether to precipitate the polymer. The precipitate was dehydrated and dried. The OI of the obtained resin was 20.5'
Met. Table 8 shows the measurement results.
樹脂１００部に対して難燃剤としてキシレニルジフェニ
ルホスフェート１５部を配合し、押出機でベレット化し
てから射出成形機により試験片を作成し、特性を評価し
た。第４表に難燃性及び物性の試験結果を示す。15 parts of xylenyl diphenyl phosphate was added as a flame retardant to 100 parts of the resin, and the mixture was formed into pellets using an extruder, and then test pieces were prepared using an injection molding machine, and their properties were evaluated. Table 4 shows the test results for flame retardancy and physical properties.
実施例６〜８
第３表に示した実施例５の単量体及び難燃剤の代りに各
々実施例６〜８の単量体及び難燃剤を使用した以外は実
施例５と同様の方法で試験片を得て、性能を評価した。Examples 6-8 The same method as Example 5 was used except that the monomers and flame retardants of Examples 6-8 were used instead of the monomers and flame retardants of Example 5 shown in Table 3. A test piece was obtained and its performance was evaluated.
又比較例４〜６として第３表に示した単量体及び難燃剤
を使用した以外は実施例５と同様の方法で試験片を作成
して性能を評価した。第４表にそれらの難燃性及び物性
の試験結果を示した。Further, as Comparative Examples 4 to 6, test pieces were prepared in the same manner as in Example 5, except that the monomers and flame retardants shown in Table 3 were used, and the performance was evaluated. Table 4 shows the test results of their flame retardancy and physical properties.
上
注ｉｌｌ離燃性ＵＬ−９４に準じた（厚さ８インチ）０
（２）熱変形温度ＪＩＳ Ｋ−６７１４に準じた。Top injection flammability according to UL-94 (thickness 8 inches) 0
(2) Heat distortion temperature according to JIS K-6714.
（３）アイゾツト衝撃強度、Ｋｆｉ（ノツチ付き］０（
４）腐食性、難燃剤を混入したベレツ）２０ｙと表面を
美しく磨いた虫ピンを試験管に入れ２３０℃の油浴に２
時間浸漬した後、虫ピンの錆の状態を目視により判定。(3) Izot impact strength, Kfi (notched) 0 (
4) Corrosive, flame retardant mixed) 20y and an insect pin with a beautifully polished surface are placed in a test tube and placed in an oil bath at 230°C.
After soaking for a period of time, the state of rust on the insect pins is visually determined.
（５）酸素指数ＡＳＴＭＤ−２６８８に準ず。(5) Oxygen index according to ASTM D-2688.
＋６）ポリフェニルボリフエニレンホスフエート〔発明
の効果〕
本発明の効果を纒めると下記の通りである。+6) Polyphenylborophenylene phosphate [Effects of the invention] The effects of the invention are summarized as follows.
（（） 本発明によって得られた成形品は難燃性と耐
熱性を兼ね備え、かつ有害な程度のハロゲンを含有しな
いため燃焼時の有毒性ガスの発生がなく、また成型時の
金型、スクリューの腐食といった不都合な問題を生じな
い利点がある。(() The molded product obtained by the present invention has both flame retardancy and heat resistance, and does not contain a harmful amount of halogen, so no toxic gas is generated during combustion, and the mold and screw during molding are This has the advantage of not causing any inconvenient problems such as corrosion.
（ロ）第２表、第４表に示すように、本発明によって製
造された成形品はＵＬ−９４の規格のｙ−。(b) As shown in Tables 2 and 4, the molded products manufactured according to the present invention meet the UL-94 standard Y-.
に合格する難燃性を示す。Demonstrates flame retardancy that passes the standard.
ｅウ 熱変形温度が大であり、アイゾツト衝撃強度が
大である。c) The heat distortion temperature is high and the Izot impact strength is high.
に）本発明によって得られた成形品は腐食性がない。b) The molded article obtained according to the present invention is not corrosive.
Claims (1)
系樹脂に、芳香族ホスフェート又は／及び芳香族ポリホ
スフェートを配合させてなる難燃性耐熱性芳香族ビニル
系樹脂組成物。 ２、マレイミド化合物がフェニルマレイミド、Ｎ−メチ
ルフェニルマレイミドである特許請求の範囲第１項記載
の難燃性耐熱性芳香族ビニル系樹脂組成物。 ３、芳香族ビニル系樹脂１００重量部に対して芳香族ホ
スフェート又は／及び芳香族ポリホスフェートを１〜３
０重量部配合してなる特許請求の範囲第１項又は第２項
記載の難 燃性耐熱性芳香族ビニル系樹脂組成物。[Claims] 1. A flame-retardant heat-resistant aromatic vinyl resin composition prepared by blending an aromatic phosphate or/and an aromatic polyphosphate into a heat-resistant aromatic vinyl resin modified with a maleimide compound. . 2. The flame-retardant and heat-resistant aromatic vinyl resin composition according to claim 1, wherein the maleimide compound is phenylmaleimide or N-methylphenylmaleimide. 3. 1 to 3 parts of aromatic phosphate or/and aromatic polyphosphate per 100 parts by weight of aromatic vinyl resin
0 parts by weight of the flame-retardant and heat-resistant aromatic vinyl resin composition according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26140786A JPS63117057A (en) | 1986-10-31 | 1986-10-31 | Flame-retardant, heat-resistant aromatic vinyl resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26140786A JPS63117057A (en) | 1986-10-31 | 1986-10-31 | Flame-retardant, heat-resistant aromatic vinyl resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63117057A true JPS63117057A (en) | 1988-05-21 |
Family
ID=17361439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26140786A Pending JPS63117057A (en) | 1986-10-31 | 1986-10-31 | Flame-retardant, heat-resistant aromatic vinyl resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63117057A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE36188E (en) * | 1989-09-20 | 1999-04-06 | General Electric Company | Polymer mixture having aromatic polycarbonate styrene I containing copolymer and/or graft polymer and a flame-retardant, articles formed therefrom |
| US6143423A (en) * | 1997-04-07 | 2000-11-07 | Shin-Etsu Chemical Co., Ltd. | Flame retardant epoxy resin compositions |
| US6177489B1 (en) | 1997-01-08 | 2001-01-23 | Shin-Etsu Chemical Co., Ltd. | Semiconductor encapsulating epoxy resin composition and semiconductor device |
| US6291556B1 (en) | 1999-03-26 | 2001-09-18 | Shin-Etsu Chemical Co., Ltd. | Semiconductor encapsulating epoxy resin composition and semiconductor device |
| US6319432B1 (en) | 1999-06-11 | 2001-11-20 | Albemarle Corporation | Bisphenol-A bis(diphenyl phosphate)-based flame retardant |
| US6399685B1 (en) | 2000-12-11 | 2002-06-04 | Albemarle Corporation | Purification of arylene polyphosphate esters |
| US6630745B1 (en) | 1999-04-26 | 2003-10-07 | Shin-Etsu Chemical Co., Ltd. | Semiconductor encapsulating epoxy resin composition and semiconductor device |
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|---|---|---|---|---|
| JPS5516082A (en) * | 1978-07-17 | 1980-02-04 | Basf Ag | Manufacture of polyynnvinylpyrrolidonee2 denatured polymer and its use |
| JPS58183729A (en) * | 1982-04-20 | 1983-10-27 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
| JPS5924736A (en) * | 1982-08-02 | 1984-02-08 | Adeka Argus Chem Co Ltd | Flame-retarding polystyrene resin composition |
-
1986
- 1986-10-31 JP JP26140786A patent/JPS63117057A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5516082A (en) * | 1978-07-17 | 1980-02-04 | Basf Ag | Manufacture of polyynnvinylpyrrolidonee2 denatured polymer and its use |
| JPS58183729A (en) * | 1982-04-20 | 1983-10-27 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
| JPS5924736A (en) * | 1982-08-02 | 1984-02-08 | Adeka Argus Chem Co Ltd | Flame-retarding polystyrene resin composition |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE36188E (en) * | 1989-09-20 | 1999-04-06 | General Electric Company | Polymer mixture having aromatic polycarbonate styrene I containing copolymer and/or graft polymer and a flame-retardant, articles formed therefrom |
| US6177489B1 (en) | 1997-01-08 | 2001-01-23 | Shin-Etsu Chemical Co., Ltd. | Semiconductor encapsulating epoxy resin composition and semiconductor device |
| US6143423A (en) * | 1997-04-07 | 2000-11-07 | Shin-Etsu Chemical Co., Ltd. | Flame retardant epoxy resin compositions |
| US6291556B1 (en) | 1999-03-26 | 2001-09-18 | Shin-Etsu Chemical Co., Ltd. | Semiconductor encapsulating epoxy resin composition and semiconductor device |
| US6630745B1 (en) | 1999-04-26 | 2003-10-07 | Shin-Etsu Chemical Co., Ltd. | Semiconductor encapsulating epoxy resin composition and semiconductor device |
| US7095125B2 (en) | 1999-04-26 | 2006-08-22 | Shin-Etsu Chemical Co., Ltd. | Semiconductor encapsulating epoxy resin composition and semiconductor device |
| US6319432B1 (en) | 1999-06-11 | 2001-11-20 | Albemarle Corporation | Bisphenol-A bis(diphenyl phosphate)-based flame retardant |
| US6399685B1 (en) | 2000-12-11 | 2002-06-04 | Albemarle Corporation | Purification of arylene polyphosphate esters |
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